SYNTHESIS AND CHARACTERIZATION OF ACETYLENIC DIOLS DERIVED FROM 1-ETHYNYLCYCLOHEXANOL AND CARBONYL COMPOUNDS
Keywords:
1-ethynylcyclohexanol, aliphatic, cyclic and aromatic ketones, catalytic system, acetylene diols, product yield, solvents.Abstract
For the first time, nucleophilic coupling reactions of 1-ethynylcyclohexanol with some ketones - cyclohexanone, acetophenone, para-chloroacetophenone, adamantanone, methylhexylketone and ethyl-n-butyl ketones were studied using the Bu4NOH/DMSO/H2O catalytic system. New acetylene diols – 1-(2-(1-hydroxycyclohexyl)ethynyl)cyclohexanol (1), 1-(3-hydroxy-3-phenylbut-1-ynyl)cyclohexanol (2), 1-(3-(4-chlorophenyl)-3-hydroxybut-1-ynyl) cyclo-hexanol(3), 1-(2-(1-hydroxyadamantanyl)ethynyl)cyclohexanol (4), 1-(3-hydroxy-3-methyldec-1-ynyl) cyclohexanol(5) and 1-(3-ethyl-3-hydroxyhept-1-ynyl) cyclohexanol (6) were synthesized in the process. The effects of the catalyst for the synthesis of acetylene diols, the nature of the solvent, the mole ratio of the starting materials, the temperature, and the duration of the reaction were systematically analyzed. The composition, structure and purity of the synthesized acetylene diols were determined by modern physical and chemical research methods.
References
1. Robert E.M., Brenda J.B. Biosynthesis and function of polyacetylenes and allied natural products. Progress in Lipid Research, 2008, no. 47, pp. 233–306. doi.org/10.1016/j.plipres.2008.02.002.
2. Kouhei H., Takuya Y., Yukio Y., Takeshi F., Akihiko K., Tetsuji O., Makoto O. Petrosiols A-E neurotrophic diyne tetraols isolated from the Okinawan sponge Petrosia strongylata. Tetrahedron, 2013, no. 69, pp. 101-106. doi.org/10.1016/j.tet.2012.10.063.
3. Dembitsky V.M. Anticancer Activity of Naturaland Synthetic Acetylenic Lipids. Lipids journal, 2006, vol. 41, no. 10, pp. 883-924. doi.org/10.1007/s11745-006-5044-3.
4. Iza Mirela Princival R.G., Jeiely Ferreira G., Teresinha Silva G., Jaciana Aguiar S., Jefferson P.L. Synthesis and in vitro evaluation of (R), (S) and (R/S)-2-hexyne-1,4-diol, a natural product produced by fungus Clitocybe catinus, and related analogs as potential anticancer agents. Bioorganic Medical Chemistry Letters, 2016, no. 26, pp. 2839–2842. doi.org/10.1016/j.bmcl.2016.04.060.
5. Jefferson L.P., Jeiely G.F. CeCl3-mediated addition of acetylenic bis-lithium salts to aldehydes and ketones: An efficient route to bis-substituted alkyne diols. Tetrahedron Letters, 2017, no. 58, pp. 3525–3528.
6. Abdeslam A., Francisco F., Miguel Y. Selective lithiation of 1,6-dihalohex-1-enes and 1,6-dihalohex-1-ynes. Tetrahedron, 2007, no. 63, pp. 6625–6634. doi.org/10.1016/j.tet.2007.03.106.
7. Masashi H., Junta E., Seiya I., Toshiaki Sh., Yasuhiro M. Chiroptical properties of 1,3-diphenylallene-anchored tetrathiafulvalene and its polymer synthesis. Beilstein Journal Organic Chemistry, 2015, no. 11, 972–979. doi.org/10.3762/bjoc.11.109.
8. Hosseinzadeh R., Abolfazli M.Kh., Mohseni M., Mohadjerani M., Lasemi Z. Efficient Synthesis and Antibacterial Activities of Some Novel 1,2,3- Triazoles Prepared from Propargylic Alcohols and Benzyl Azides. Journal of Heterocyclic Chemistry, 2014, vol. 51, pp. 1298- 1305. doi 10.1002/jhet.1680.
9. Bhanuchandra M., Malleswara R.K., Akhila K. S. Silver(I)-Catalyzed Reaction between Pyrazole and Propargyl Acetates: Stereoselective Synthesis of the Scorpionate Ligands (E)-Allyl-gem-dipyrazoles (ADPs). The journal of Organic chemistry, 2013, no. 78, pp. 11824−11834. doi.org/10.1021/jo401867e.
10 Otamukhamedova G., Ziyadullaev O., Shmid Elena, Maniecki Tomash Enantioselective alkynylation of some cyclical ketones by 3,3′-diphenylbinaphtol dilithium. Chemistry and Chemical Engineering, 2019, no. 6, pp. 30-36.
11. Buriyev F.X., Ziyadullaev O.E. Synthesis of aromatic acetylene alcohols and their vinyl ethers by various methods. European Journal of Research and Reflection in Educational Sciences, 2020, vol. 8, no. 3, pp.-190-195.
12. Kana T., Kenji K., Tomonori I., Shunsuke K., Makoto N. Lithium acetylides as alkynylating reagents for the enantioselective alkynylation of ketones catalyzed by lithium binaphtholate. Chemical Communications, 2011, vol. 47, pp. 5614–5616. doi.org/10.1039/C1CC10734H.
13. Bora S., Matias F.M., Carlo R., Mohamed A. One-Pot Alkynylation of Azaaryl Aldehydes and pontaneous Base-Free Rearrangement into Enone Esters: An Autoinductive Mechanism. European Journal of Organic Chemistry, 2018, pp. 1491–1495. doi.org/10.1002/ejoc.201701566.
14. Hiroshi M., Yuki N., Ryosuke M. A Grignard-Type Phase-Vanishing Method: Generation of Organomagnesium Reagent and Its Subsequent Addition to Carbonyl Compounds. New York – Synlett, 2015, vol. 26, pp. 1276–1280. doi: 10.1055/s-0034-1380381.
